Catalytic Asymmetric Intramolecular Hydroacylation with Rhodium/Phosphoramidite–Alkene Ligand Complexes

Vaulted Biaryls in Catalysis: A Structure–Activity Relationship Guided Tour of the Immanent Domain of the VANOL Ligand

“…The vaulted biaryl ligands VANOL and VAPOL have been demonstrated to be effective in a variety of useful catalytic asymmetric reactions including amidation of imines,1 aminoallylation of aldehydes,2 aza‐Darzens reaction3 cis ‐aziridination of imines4, 5 trans ‐aziridination of imines,4q, 6 Baeyer–Villiger reactions,7 benzoyloxylation of aryloxindoles,8 desymmetrization of aziridines,9 Diels–Alder reactions,10 heteroatom Diels–Alder reactions,11 hydroarylation of alkenes,12 hydrogenation of alkenes,13 imidation of imines,14 Mannich reactions,15 multicomponent aziridination of aldehydes,16 Petasis reaction,17 propargylation of ketones,18 reduction of imines,19 chlorination and Michael reactions of oxindoles,20 hydroacylation of alkenes,21 pinacol rearrangement,22 reduction of aminals23 and Michael addition of alkynes 24…”

Intermolecular Markovnikov-Selective Hydroacylation of Olefins Catalyzed by a Cationic Ruthenium–Hydride Complex

“…Since most of these catalytic methods generally exhibit anti -Markovnikov selectivity in forming linear ketone products, much research efforts has been directed to develop Markovnikov-selective hydroacylation reaction to form the branched ketone products. 7,8 Even though Markovnikov-selective asymmetric hydroacylation reaction has been achieved under intramolecular conditions, 8 a relatively few examples of intermolecular Markovnikov-selective hydroacylation methods have been reported. Moreover, the substrate scope for the Markovnikov-selective hydroacylation reaction has been generally limited to either aldehydes with heteroatom chelate group or activated olefin substrates.…”

Rhodium‐Catalyzed Enantioselective Intramolecular Hydroacylation of Trisubstituted Alkenes

“…[2][3][4][5] However,i ntramolecular alkene hydroacylation reactions that employ higher order alkenes remainrare. [4] In addition, rhodium-and cobalt-catalyzed hydroacylations of 1,1-disubstituted 2-vinylbenzaldehydeso ccur to generate 3-substituted indan-1-onesw ith high enantioselectivities. Rhodium-catalyzed hydroacylations of 4-pentenals are established methods for formingc yclopentanone derivatives, in manyc ases with high diastereo-and/ore nantioselectivity.…”